Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme

ABSTRACT

There is provided a non-phosphate builder-containing detergent composition formulated with a surfactant, a water-soluble organic polymeric polycarboxylic compound, a chelant, an amylase and a source of alkalinity, wherein (a) said water-soluble organic polymeric polycarboxylic compound is in amount less than 3% by weight, (b) said chelant is in amount from 0.1% to 10% by weight, (c) said amylase is in amount from 0.001% to 5% by weight, and (d) said alkalinity source has the capacity to deliver alkalinity to a wash solution as measured by the alkalinity release test described herein, such that the % weight NaOH equivalent of the composition is greater than 8.0% by weight of the composition. Also provided herein is a method for reducing fabric encrustation which comprises contacting the fabric with an effective amount of an aqueous solution of said detergent composition.

TECHNICAL FIELD

The present invention relates to non-phosphate builder-containingdetergent compositions. More particularly, the invention relates tonon-phosphate detergent compositions, comprising a surfactant, awater-soluble organic polymeric polycarboxylic compound, a chelant andan amylase together with an alkalinity source, which provide effectivesoil/stain removal.

BACKGROUND OF THE INVENTION

The satisfactory removal of soils/stains is a particular challenge tothe formulator of a detergent composition for use in a washing processsuch as laundry or machine dishwashing process.

Traditionally, the removal of soils/stains has been achieved by the useof bleach components and also by enzyme components.

Amylases are known as effective soil/stain removal agents, for example,in the removal of starch stains such as chocolate.

Polymeric polycarboxylic acid components are also known in detergentcompositions as effective soil suspension and anti-encrustation agents.

Chelating agents are known in detergent compositions for their abilityto assists in the removal of organic stains during the laundry process.

Phosphorus containing compounds such as sodium tripolyphosphate haveeffective builder properties; however environmental concerns have madethe use of phosphorus containing compounds less attractive in detergentcompositions.

A problem encountered with the use of enzymes as components ofdetergents is that enzyme activity in the wash may be affected by thepresence of other detergent components in the wash solution.

A problem encountered with the use of high level of polymericpolycarboxylic acid compounds when in presence of high level of analkaline source is the propensity of these polycarboxylic compounds tolead to an overbuilt situation which may impair the amylase activity andthen leads to poor soil/stain removal performance. Furthermore, highlevels of polymeric polycarboxylic acid compounds increase the cost ofthe detergents to the consumer. On the other hand, low levels ofpolymeric polycarboxylic acid compounds may lead to encrustation,especially when using high levels of carbonate/silicate alkalinity in anon phosphate builder-containing detergent composition.

The detergent formulator thus faces the challenge of formulating anenvironmentally friendly product which maximises soil/stain removal,which minimises the occurence of any unwelcome encrustation, whichavoids degradation of the detergent components and which is alsoinexpensive.

U.S. Pat. No. 4,919,845 discloses a phosphate free detergent compositioncomprising a polycarboxylate compound and a hydroxy-ethylene 1,1diphosphonate (HEDP) chelant. Particularly disclosed are high levels ofpolycarboxylates 3% to 4% by weight, 0.22% to 0.4% by weight of HEDP,12.5% by weight of an alkalinity source and 0.5% by weight of an enzymegranulate. The described composition is asserted to provide effectiveantiencrustation benefits.

The Applicants have found that the occurence of encrustation effectsarising from use of polymeric polycarboxylic compounds at low levels arerelated to the level of alkalinity present into the wash solution, thealkalinity being produced by the alkaline components of the composition.A high level of an alkalinity source in the detergent composition tendsto exarcerbate the encrustation problem, as does a high level in thewash solution. Whilst reducing the level of alkalinity employed in thewash tends to ameliorate these problems; this is accompanied by a markednegative effect on the stain/soil removal ability.

The Applicants have now surprisingly found that where a non phosphatebuilder-containing detergent composition containing a surfactant, awater-soluble organic polymeric polycarboxylic compound, a chelant andan amylase together with an alkalinity source is employed, an enhancedstain/soil removal and a reduced encrustation may be obtained.

The Applicants have found that the further addition of compoundsenhances the overall soil/stain removal performance. Such additionalcompounds may be selected from proteases, a source of hydrogen peroxidewith or without peroxyacid bleach precursors and mixtures thereof.

It is therefore an object of the present invention to providecompositions suitable for use in laundry and machine dishwashing methodsproducing enhanced stain removal.

It is a further object of the invention to provide compositions for usein laundry and machine dishwashing methods wherein said compositionsshow less propensity to cause encrustation.

SUMMARY OF THE INVENTION

According to the present invention there is provided a non-phosphatebuilder-containing detergent composition formulated with a surfactant, awater-soluble organic polymeric polycarboxylic compound, a chelant, anamylase and a source of alkalinity, wherein

a) said water-soluble organic polymeric polycarboxylic compound is inamount less than 3% by weight,

b) said chelant is in amount from 0.1% to 10% by weight,

c) said amylase is in amount from 0.001% to 5% by weight, and

d) said alkalinity source has the capacity to deliver alkalinity to awash solution as measured by the alkalinity release test describedherein, such that the % weight NaOH equivalent of the composition isgreater than 8.0% by weight of the composition.

Also provided herein is a method for reducing fabric encrustation whichcomprises contacting the fabric with an effective amount of an aqueoussolution of said detergent composition.

Alkalinity is the combining power of a base measured by the maximumnumber of equivalents of an acid with which it can react to form a salt.In solution, it represents the carbonates and silicates in the water andis determined by titration with standard datum points.

For the purpose of the invention, alkalinity is defined as the weightequivalent of sodium hydroxide (NaOH) needed to be delivered into thewash to neutralise an equivalent amount of hydrochloric acid.

DETAILED DESCRIPTION OF THE INVENTION

Water-soluble Organic Polymeric Polycarboxylic Compounds

An essential component of the invention is one or more water-solubleorganic polymeric polycarboxylic compounds. Preferably these compoundsare a homo- or co-polymeric polycarboxylic compounds and most preferablya co-polymeric polycarboxylic compounds in which the acid monomer ofsaid polycarboxylic compound comprises at least two carboxyl groupsseparated by not more than two carbon atoms. Salts of thesepolycarboxylic compounds are also considered herein.

Polymeric polycarboxylate compounds are utilised at levels less than 3%,preferably from 0.1% to 3% and more preferably less than 1% by weight.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates are selected from acrylic acid,maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconiticacid, mesaconic acid, citraconic acid and methylenemalonic acid. Thepresence in the polymeric polycarboxylates herein of monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than 40% by weight.

Polymeric polycarboxylate materials can also optionally include furthermonomeric units such as nonionic spacing units. For example, suitablenonionic spacing units may include vinyl alcohol or vinyl acetate.

Particularly preferred polymeric polycarboxylates are co-polymersderived from monomers of acrylic acid and maleic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom 2,000 to 10,000, more preferably from 4,000 to 7,000 and mostpreferably from 4,000 to 5,000. Water-soluble salts of suchacrylic/maleic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967. The ratio of acrylate to maleatesegments in such copolymers will generally range from 30:1 to 1:1, morepreferably from 10:1 to 2:1. Soluble acrylate/maleate copolymers of thistype are known materials which are described in European PatentApplication No. 66915, published Dec. 15, 1982, as well as in EP193,360, published Sep. 3, 1986, which also describes such polymerscomprising hydroxypropylacrylate. Of these acrylic/maleic-basedcopolymers, the water-soluble salts of copolymers of acrylic acid andmaleic acid are preferred.

Another class of polymeric polycarboxylic acid compounds suitable forthe purpose of the invention are the homo-polymeric polycarboxylic acidcompounds derived from acrylic acid. The average molecular weight ofsuch homo-polymers in the acid form preferably ranges from 2,000 to100,000, more preferably from 3,000 to 75,000, most preferably from4,000 to 65,000.

A further example of polymeric polycarboxylic compounds suitable for thepurpose of the invention include the maleic/acrylic/vinyl alcoholterpolymers. Such materials are also disclosed in EP 193,360, including,for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another example of polymeric polycarboxylic compounds suitable for thepurpose of the invention include the biodegradable polyaspartic acid andpolyglutamic acid compounds.

Chelants

An essential component of the invention is a chelating agent. Chelatingagents generally comprise from 0.1% to 10% by weight of the compositionsherein. More preferably, if utilized, the chelating agents will comprisefrom 0.1% to 3.0% by weight of such compositions.

Chelating agents can be selected from organic phosphonates, aminocarboxylates, polyfunctionally-substituted aromatic compounds,nitriloacetic acid and mixtures thereof. Without intending to be boundby theory, it is believed that the benefit of these materials is due inpart to their exceptional ability to remove transition metal ions suchas iron and manganese ions from washing solutions by formation ofsoluble chelates.

Organic phosphonates suitable for use as chelating agents in thecompositions of the invention, are selcted from ethylenediaminetetrakis(methylenephosphonates) available under the trademark DEQUEST fromMonsanto, diethylene triamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylene diamine tetra(methylene phosphonate), α-hydroxy-2 phenyl ethyl diphosphonate,methylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate andhydroxy-ethylene 1,1 diphosphonate.

Preferably, these amino phosphonates do not contain alkyl or alkenylgroups with more than 6 carbon atoms.

Amino carboxylates chelating agents include ethylenediaminetetracetates,ethylenediamine disuccinate, N-hydroxyethylethylenediamine triacetates,2-hydroxypropylene diamine disuccinate, nitrilotriacetates,ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,ethylene triamine pentaacetate, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Preferred amino carboxylates chelants for use herein are ethylenediaminedisuccinate ("EDDS"), especially the S,S! isomer as described in U.S.Pat. No. 4,704,233, ethylenediamine-N,N'-diglutamate (EDDG) and2-hydroxypropylene-diamine-N,N'-disuccinate (HPDDS) compounds. A mostpreferred amino carboxylate chelant is ethylenediamine disuccinate.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044. Preferredcompounds of this type in acid form are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

Of these, preferred chelants for the purpose of the invention are thediphosphonate derivatives of the organic phosphonate chelants selectedfrom α-hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate,hydroxy 1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2dihydroxyethane 1,1 diphosphonate and hydroxy-ethylene 1,1diphosphonate. A most preferred is hydroxy-ethylene 1,1 diphosphonate.

Amylases

Another essential component of the invention is an amylase.

Amylase enzyme are incorporated into the composition in accordance withthe invention at a level of from 0.001% to 5% active enzyme by weight ofthe composition.

Preferred amylases include, for example, α-amylases obtained from aspecial strain of B licheniformis, described in more detail inGB-1,269,839 (Novo). Preferred commercially available amylases includefor example, those sold under the tradename Rapidase by Gist-Brocades,and those sold under the tradename Termamyl and BAN by Novo IndustriesA/S. A most preferred amylase is Termamyl.

Alkalinity Source

An essential component of the detergent composition is an alkalinitysource.

For the purpose of the invention, alkalinity is defined as the weightequivalent of sodium hydroxide (NaOH) needed to be delivered into thewash to neutralise an equivalent amount of hydrochloric acid.

To enable practical comparison of the relative capacity of compositionscontaining different alkaline components to deliver alkalinity to a washsolution it is useful to express the alkalinity released on addition ofthe compositions to the wash solution in terms of % weight equivalent ofNaOH. That is, in terms of the % weight of NaOH which would haveequivalent `alkaline effect`, e. g. in neutralising acid species, tothat of the alkalinity species actually released when the composition isadded to the wash. For uniform comparison it is also then useful todefine standard wash solution characteristics. Thus, the capacity todeliver alkalinity to a wash solution is herein characterized byreference to a representative test method now described.

Alkalinity Release Test Method

A 1 g sample of detergent composition is added to 100 ml of distilledwater at a temperature of 30° C. with stirring at 150 rpm using amagnetic stirrer of size 2 cm, thus providing a 1% detergent solution,as would be a typical concentration of a laundry wash solution. Thesolution is titrated against a standard HCl solution using any suitabletitration method. Commonly known acid-base titration methods employingcolorimetric end-point determination methods, for example using chemicalend-point indicators are particularly suitable. Thus, the number ofmoles of HCl which the detergent solution is capable of neutralising isobtained. For the avoidance of doubt, `neutralising` in this context isdefined to mean titrating to pH 7. This number will be equivalent to thenumber of moles of alkalinity, expressed as NaOH equivalent, present inthe detergent solution. Thus, the % weight equivalent NaOH present inthe sample of the detergent composition may be calculated as:

    % weight equivalent NaOH=100×number of moles NaOH equivalent in solution×Mw of NaOH

Theoretical Maximum Alkalinity

Where the compositional make up of a detergent product is known, it ispossible to calculate the theoretical maximum alkalinity, expressed as %weight equivalent of NaOH, which the product could provide to a solutionas the sum over each alkaline species of:

    % weight (alkaline species).Mw(NaOH.n/Mw(alkaline species)

where n is the formal negative charge carried by the alkaline species.

As an example, a composition containing 12% sodium carbonate isequivalent to a theoretical maximum of 9.06% NaOH, obtained as(12×40×2)/106, since this amount of NaOH in the composition wouldtheoretically neutralise the same amount of acid as the 12% sodiumcarbonate alkaline component.

Alkalinity Requirement

In accord with the present invention, the alkalinity source is presentin the detergent composition such that the capacity to deliveralkalinity to a wash solution measured by the given test method is suchthat the % weight NaOH equivalent of the composition is greater than8.0%, preferably at least 10.6% and most preferably 14.6% by weight ofthe composition.

The alkalinity source is preferably selected from alkali metalcarbonates, alkali metal silicates and mixtures thereof.

Suitable alkali metal carbonates include the alkaline earth and alkalimetal carbonates, including sodium carbonate and sesqui-carbonate andmixtures thereof with ultra-fine calcium carbonate as disclosed inGerman Patent Application No. 2,321,001 published on Nov. 15, 1973.

Suitable silicates include the alkali metal silicate SiO₂ :Na₂ O with aratio of from 1.0 to 2.8 and 1.6:1 ratio being more preferred. Thesilicates may be in the form of either the anhydrous salt or a hydratedsalt. Sodium silicate with an SiO₂ :Na₂ O ratio of 1.6:1 is the mostpreferred silicate.

Other compounds which provide free alkalinity in aqueous solution mayalso be used. Such compounds include the crystalline layered silicateand/or aluminosilicate compounds as described herein after, but also thebicarbonates, hydroxides, borates and phosphates.

Additional Components

The detergent composition of the invention will, of course contain oneor more surfactants and additional compounds for enhancing the soilremoval performance.

Such compounds include the proteases, a source of hydrogen peroxide withor without peroxyacid bleach precursors, builders and conventionaldetersive adjuncts.

Detersive Surfactants

The total amount of surfactants will be generally up to 70%, typically 1to 55%, preferably 1 to 30%, more preferably 5 to 25% and especially 10to 20% by weight of the total composition.

Nonlimiting examples of surfactants useful herein include theconventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") and primary,branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), the C₁₀ -C₁₈secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)x(CHOSO₃ ⁻ M⁺)CH₃ and CH₃ (CH₂)_(y) (CHOSO₃ ⁻ M⁺) CH₂ CH₃ where x and (y+1) areintegers of at least 7, preferably at least 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates ("AExS"; especiallyEO 1-7 ethoxy sulfates), C₁₀ -C₁₈ alkyl alkoxy carboxylates (especiallythe EO 1-5 ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers, the C₁₀ -C₁₈alkyl polyglycosides and their corresponding sulfated polyglycosides,and C₁₂ -C₁₈ alpha-sulfonated fatty acid esters. If desired, theconventional nonionic and amphoteric surfactants such as the C₁₂ -C₁₈alkyl ethoxylates ("AE"), including the so-called narrow peaked alkylethoxylates and C₆ -C₁₂ alkyl phenol alkoxylates (especially ethoxylatesand mixed ethoxy/propoxy), C₁₂ -C₁₈ betaines and sulfobetaines("sultaines"), C₁₀ -C₁₈ amine oxides, and the like, can also be includedin the overall compositions. The C₁₀ -C₁₈ N-alkyl polyhydroxy fatty acidamides can also be used. Typical examples include the C₁₂ -C₁₈N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactantsinclude the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀ -C₁₈N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂ -C₁₈glucamides can be used for low sudsing. C₁₀ -C₂₀ conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C₁₀ -C₁₆soaps may be used.

Other suitable surfactants suitable for the purpose of the invention arethe anionic alkali metal sarcosinates of formula:

    R--CON(R.sup.1)CH.sub.2 COOM

wherein R is a C₉ -C₁₇ linear or branched alkyl or alkenyl group, R₁ isa C₁ -C₄ alkyl group and M is an alkali metal ion. Preferred examplesare the lauroyl, cocoyl (C₁₂ -C₁₄), myristyl and oleyl methylsarcosinates in the form of their sodium salts.

Still another class of surfactant which may be suitable for the purposeof the invention are the cationic surfactant. Suitable cationicsurfactants include the quatemary ammonium surfactants selected frommono C₆ -C₁₆, preferably C₆ -C₁₀ N-alkyl or alkenyl ammonium surfactantswherein the remaining N positions are substituted by methyl,hydroxyethyl or hydroxypropyl groups.

Mixtures of anionic and nonionic surfactants are especially useful.Other conventional useful surfactants are listed in standard texts.

Proteases

When used, the compositions herein will typically comprise from 0.001%to 5% active protease by weight of the composition.

Preferred commercially available protease enzymes include those soldunder the tradenames Alcalase, Savinase, Primase, Durazym, and Esperaseby Novo Industries A/S (Denmark), those sold under the tradenameMaxatase, Maxacal and Maxapem by Gist-Brocades, those sold by GenencorInternational, and those sold under the tradename Opticlean and Optimaseby Solvay Enzymes. Mixture of the herein before described proteases maybe used.

A most preferred protease is Savinase.

Source of Hydrogen Peroxide

An essential component of the detergent composition is a source ofhydrogen peroxide. The source of hydrogen peroxide is normallyincorporated at a level of at least 0.5% by weight, more preferably from4% to 15% by weight and most preferably from 4% to 10% by weight of thecomposition.

Said source of hydrogen peroxide is a slow releasing source. The slowrelease of hydrogen peroxide source relative to that of the protease issuch that the time to achieve a concentration that is 50% of theultimate concentration of said enzyme is less than 120 seconds,preferably less than 90 seconds, more preferably less than 60 seconds,and the time to achieve a concentration that is 50% of the ultimateconcentration of said hydrogen peroxide source is more than 180 seconds,preferably from 180 to 480 seconds, more preferably from 240 to 360seconds. Preferably the time to achieve a concentration that is 50% ofthe ultimate concentration of said enzyme is at least 100 seconds lessthan the time to achieve a concentration that is 50% of the ultimateconcentration for the hydrogen peroxide source.

Such slow release kinetic is more particularly described in pending GBApplication No. 9407533.0.

In this respect, a preferred source of hydrogen peroxide is an inorganicperhydrate. A preferred perhydrate is perborate tetrahydrate of nominalformula NaBO₂ H₂ O₂.3H₂ O. The inorganic perhydrate will normally be inthe form of the sodium salt. More preferably, the source of hydrogenperoxide consists of at least 90% by weight of a perborate tetrahydrate.

Alternatively, other perhydrate compounds may be used in addition or inplace of the perborate tetrahydrate together with appropriate means,such as coating, coagglomeration, to obtain a slow release of hydrogenperoxide. Such compounds can include perborate monohydrate,percarbonate, perphosphate, persilicate salts and mixtures thereof.

Of these compounds, a preferred perhydrate is percarbonate. Coarsepercarbonate materials, of average particle size greater than 600micrometers and preferably greater than 750 micrometers, may be used.Preferably, these percarbonate materials are coated with substanceswhich are sparingly soluble in water. Water insoluble coating materialsmay be selected from fatty acid, polymers, hydrophobic silicas, waxesand magnesium silicates and mixtures thereof. Percarbonate materialswhich are exclusively coated with water-soluble substances such ascitrates, borosilicates, borate derivatives, sodium carbonate orsodium/magnesium sulphate are not preferred.

When percarbonate is used, the source of hydrogen peroxide consists ofat least 90% by weight of a percarbonate having a particle size of atleast 600 micrometers and coated with water-insoluble materials.

Mixtures of any of the herein before described perhydrate compounds canalso be used.

Preferably, the total amount of available oxygen present in thecomposition which include the available oxygen provided by the source ofhydrogen peroxide with or without peroxyacid bleach precursors is lessthan 1.5% by weight. A method for determining AvO₂ levels is disclosedin European Patent Application No.93870004.4.

Organic Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogenperoxide in a perhydrolysis reaction to produce a peroxyacid. Generallyperoxyacid bleach precursors may be represented as ##STR1## where L is aleaving group and X is essentially any functionality, such that onperhydrolysis the structure of the peroxyacid produced is ##STR2##

Peroxyacid bleach precursor compounds are preferably incorporated at alevel of from 0.01% to 10% by weight, more preferably from 3% to 10% byweight, most preferably from 5% to 9% by weight of the precursorcomposition.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e.g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of: ##STR3##and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizinggroup. Any of R¹, R³ and R⁴ may be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy, halogen,amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.

The preferred solubilizing groups are --SO₃ ⁻ M⁺, --CO₂ ⁻ M⁺, --SO₄ ⁻M⁺, --N⁺ (R³)₄ X-- and O<--N(R³)₃ and most preferably --SO₃ ⁻ M⁺ and--CO₂ ⁻ M⁺ wherein R³ is an alkyl chain containing from 1 to 4 carbonatoms, M is a cation which provides solubility to the bleach activatorand X is an anion which provides solubility to the bleach activator.Preferably, M is an alkali metal, ammonium or substituted ammoniumcation, with sodium and potassium being most preferred, and X is ahalide, hydroxide, methylsulfate or acetate anion.

Suitable peroxyacid bleach precursor materials are compounds whichcomprise at least one acyl group forming the peroxyacid moiety bonded toa leaving group through an --O-- or --N-- linkage.

These can be selected from a wide range of classes that includeanhydrides, esters, imides, lactams and acylated derivatives ofimidazoles and oximes. Examples of useful materials within these classesare disclosed in GB-A-1586789. Suitable esters are disclosed inGB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

A preferred class of bleach precursor is the class of N-acylatedprecursors of which TAED is the preferred one.

Peroxyacid precursor compositions containing mixtures of any of theprecursors hereinafter disclosed are also contemplated by the presentinvention.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid onperhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include thesubstituted and unsubstituted benzoyl oxybenzene sulfonates, includingfor example benzoyl oxybenzene sulfonate: ##STR4##

Also suitable are the benzoylation products of sorbitol, glucose, andall saccharides with benzoylating agents, including for example:##STR5##

Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substitutedureas. Suitable imidazole type perbenzoic acid precursors includeN-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acylgroup-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides,the benzoyl tetraacyl peroxides, and the compound having the formula:##STR6##

Phthalic anhydride is another suitable perbenzoic acid precursorcompound herein: ##STR7##

Suitable N-acylated precursor compounds of the lactam class aredisclosed generally in GB-A-855735. Whilst the broadest aspect of theinvention contemplates the use of any lactam useful as a peroxyacidprecursor, preferred materials comprise the caprolactams andvalerolactams.

Suitable caprolactam bleach precursors are of the formula: ##STR8##wherein R⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl groupcontaining from 1 to 12 carbon atoms, preferably from 6 to 12 carbonatoms.

Suitable valero lactams have the formula: ##STR9## wherein R⁶ is H or analkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbonatoms, preferably from 6 to 12 carbon atoms. In highly preferredembodiments, R⁶ is selected from phenyl, heptyl, octyl, nonyl,2,4,4-trimethylpentyl, decenyl and mixtures thereof.

The most preferred materials are those which are normally solid at <30°C., particularly the phenyl derivatives, ie. benzoyl valerolactam,benzoyl caprolactam and their substituted benzoyl analogues such aschloro, amino alkyl, alkyl, aryl and alkyloxy derivatives.

Caprolactam and valerolactam precursor materials wherein the R⁶ moietycontains at least 6, preferably from 6 to about 12, carbon atoms provideperoxyacids on perhydrolysis of a hydrophobic character which affordnucleophilic and body soil clean-up. Precursor compounds wherein R⁶comprises from 1 to 6 carbon atoms provide hydrophilic bleaching specieswhich are particularly efficient for bleaching beverage stains. Mixturesof `hydrophobic` and `hydrophilic` caprolactams and valero lactams,typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be usedherein for mixed stain removal benefits.

Perbenzoic Acid Derivative Precursors

Perbenzoic acid derivative precursors provide substituted perbenzoicacids on perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include anyof the herein disclosed perbenzoic precursors in which the benzoyl groupis substituted by essentially any non-positively charged (ie;non-cationic) functional group including, for example alkyl, hydroxy,alkoxy, halogen, amine, nitrosyl and amide groups.

A preferred class of substituted perbenzoic acid precursor compounds arethe amide substituted compounds of the following general formulae:##STR10## wherein R¹ is an aryl or alkaryl group with from 1 to 14carbon atoms, R² is an arylene, or alkarylene group containing from 1 to14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms and L can be essentially any leavinggroup. R¹ preferably contains from 6 to 12 carbon atoms. R² preferablycontains from 4 to 8 carbon atoms. R¹ may be aryl, substituted aryl oralkylaryl containing branching, substitution, or both and may be sourcedfrom either synthetic sources or natural sources including for example,tallow fat. Analogous structural variations are permissible for R². Thesubstitution can include alkyl, aryl, halogen, nitrogen, sulphur andother typical substituent groups or organic compounds. R⁵ is preferablyH or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms intotal. Amide substituted bleach activator compounds of this type aredescribed in EP-A-0170386.

Cationic Peroxyacid precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting theperoxyacid part of a suitable peroxyacid precursor compound with apositively charged functional group, such as an ammonium or alkylammmonium group, preferably an ethyl or methyl ammonium group. Cationicperoxyacid precursors are typically present in the solid detergentcompositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substituted derivative thereof, precursorcompound as described hereinbefore. Altematively, the peroxyacidprecursor compound may be an alkyl percarboxylic acid precursor compoundor an amide substituted alkyl peroxyacid precursor as describedhereinafter.

Cationic peroxyacid precursors are described in U.S. Pat. Nos.4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852;5,093,022; 5,106,528; U.K 1,382,594; EP 475,512, 458,396 and 284,292;and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UKPatent Application No. 9407944.9 and U.S. patent application Ser. Nos.08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium oralkyl ammonium substituted alkyl or benzoyl oxybenzene suffonates,N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoylperoxides.

A preferred cationically substituted benzoyl oxybenzene sulfonate is the4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzenesulfonate: ##STR11##

A preferred cationically substituted alkyl oxybenzene sulfonate has theformula: ##STR12##

Preferred cationic peroxyacid precursors of the N-acylated caprolactamclass include the trialkyl ammonium methylene benzoyl caprolactams,particularly trimethyl ammonium methylene benzoyl caprolactam: ##STR13##

Other preferred cationic peroxyacid precursors of the N-acylatedcaprolactam class include the trialkyl ammonium methylene alkylcaprolactams: ##STR14## where n is from 0 to 12.

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethylammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Benzoxazin organic peroxyacid precursors Also suitable are precursorcompounds of the benzoxazin-type, as disclosed for example inEP-A-332,294 and EP-A-482,807, particularly those having the formula:##STR15## including the substituted benzoxazins of the type ##STR16##wherein R¹ is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R², R³,R⁴, and R⁵ may be the same or different substituents selected from H,halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino,COOR⁶ (wherein R⁶ is H or an alkyl group) and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is: ##STR17##Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acidon perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide typeinclude the N,N-N',N' tetra acetylated alkylene diamines wherein thealkylene group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium3,5,5-trimethyl hexanoyloxybenzene sulfonate (ISONOBS), sodiumnonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate(ABS) and pentaacetyl glucose.

Amide Substituted Alkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are alsosuitable, including those of the following general formulae: ##STR18##wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is analkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or analkyl group containing 1 to 10 carbon atoms and L can be essentially anyleaving group. R¹ preferably contains from 6 to 12 carbon atoms. R²preferably contains from 4 to 8 carbon atoms. R¹ may be straight chainor branched alkyl containing branching, substitution, or both and may besourced from either synthetic sources or natural sources including forexample, tallow fat. Analogous structural variations are permissible forR². The substitution can include alkyl, halogen, nitrogen, sulphur andother typical substituent groups or organic compounds. R⁵ is preferablyH or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms intotal. Amide substituted bleach activator compounds of this type aredescribed in EP-A-0170386.

Preferred amide substituted alkyl peroxyacid precursor compounds are(6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene sulfonate and (6-decanamido-caproyl)oxybenzene sulfonate andmixture thereof.

More preferred peroxyacid bleach precursors compounds for use in theinvention are selected from N,N-N',N' tetra acetyl ethylene diamine,3,5,5-trimethyl hexanoyl oxybenzene sulfonate, nonanoyl oxybenzenesulfonate, amide substituted perbenzoic acid precursor compounds, amidesubstituted alkyl peroxyacid precursors and mixtures thereof.

A most preferred peroxyacid bleach precursor is N,N-N',N' tetra acetylethylene diamine.When used TAED will preferably be at a level of from0.5% to 2.5% by weight.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can optionally be utilized herein. One type of non-oxygenbleaching agent of particular interest includes photoactivated bleachingagents such as the sulfonated zinc and/or aluminum phthalocyanines. SeeU.S. Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from 0.025% to 1.25%, byweight, of such bleaches, especially sulfonate zinc phthalocyanine.

Builders

Detergent builders can optionally be included in the compositions hereinto assist in controlling mineral hardness. Inorganic as well as organicbuilders can be used. Builders are typically used in fabric launderingcompositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least 1% builder. Granularformulations typically comprise from 10% to 80%, more typically from 15%to 50% by weight, of the detergent builder. Lower or higher levels ofbuilder, however, are not meant to be excluded.

These can include, but are not restricted to phytic acid, silicates,alkali metal carbonates (including bicarbonates and sesquicarbonates),sulphates, aluminosilicates, monomeric polycarboxylates, homo orcopolymeric polycarboxylic acids or their salts in which thepolycarboxylic acid comprises at least two carboxylic radicals separatedfrom each other by not more than two carbon atoms. Examples of silicatebuilders are the crystalline layered silicates, such as the layeredsodium silicates described in U.S. Pat. No. 4,664,839. NaSKS-6 is thetrademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂ Si₂ O₅ morphology form of layered silicate. It can be preparedby methods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x) O_(2x+1).yH₂ O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used herein. Various other layeredsilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as thealpha, beta and gamma forms. As noted above, the delta-Na₂ Si₂ O₅(NaSKS-6 form) is most preferred for use herein. Other silicates mayalso be useful such as for example magnesium silicate, which can serveas a crispening agent in granular formulations, as a stabilising agentfor oxygen bleaches, and as a component of suds control systems.

Aluminosilicate builders are especially useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    Na.sub.z  (AlO.sub.2).sub.z (SiO.sub.2).sub.y !.xH2O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to 0.5, and x is an integer from 15 to 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669. Preferredsynthetic crystalline aluminosilicate ion exchange materials usefulherein are available under the designations Zeolite A, Zeolite P (B),Zeolite MAP and Zeolite X. In an especially preferred embodiment, thecrystalline aluminosilicate ion exchange material has the formula:

    Na.sub.12  (AlO.sub.2).sub.12 (SiO.sub.2).sub.12 !.xH.sub.2 O

wherein x is from 20 to 30, especially 27. This material is known asZeolite A. Dehydrated zeolites (x=0-10) may also be used herein.Preferably, the aluminosilicate has a particle size of 0.1-10 microns indiameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralised salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in U.S. Pat. No. 3,128,287 and U.S. Pat. No. 3,635,830. Seealso "TMS/TDS" builders of U.S. Pat. No. 4,663,071. Suitable etherpolycarboxylates also include cyclic compounds, particularly alicycliccompounds, such as those described in U.S. Pat. Nos. 3,923,679;3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, or acrylic acid, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, thevarious alkali metal, ammonium and substituted ammonium salts ofpolyacetic acids such as ethylenediamine tetraacetic acid andnitrilotriacetic acid, as well as polycarboxylates such as melliticacid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and solublesalts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the compositions containing the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984. Useful succinic acid buildersinclude the C₅ -C₂₀ alkyl and alkenyl succinic acids and salts thereof.A particularly preferred compound of this type is dodecenylsuccinicacid. Specific examples of succinate builders include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Laurylsuccinates are thepreferred builders of this group, and are described in EP 0,200,263.

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226and in U.S. Pat. No. 3,308,067. See also U.S. Pat. No. 3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

Conventional Detersive Adjuncts

The compositions herein can optionally include one or more otherdetergent adjunct materials or other materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the detergent composition (e.g.,perfumes, colorants, dyes, etc.). The following are illustrativeexamples of such adjunct materials.

Enzymes

Other enzymes than amylases and proteases may be used. These includecellulases, lipases, peroxidase, endoglucanase and mixtures thereof.

These enzymes may be incorporated into the composition in accordancewith the invention at a level of from 0.001% to 5% active enzyme byweight of the composition.

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,which discloses fungal cellulase produced from Humicola insolens andHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk (Dolabella Auricula Solander). Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.ENDO A, CAREZYME both from Novo Industries A/S are especially useful.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open to public inspection on Feb. 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd.,Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P." Other commercial lipases include Amano-CES,lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicolalanuginosa and commercially available from Novo (see also EP 341,947) isa preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching," i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in EP-A-0,424,398.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139. Enzymes are further disclosed in U.S. Pat. No. 4,101,457 andin U.S. Pat. No. 4,507,219. Enzyme materials useful for liquid detergentformulations, and their incorporation into such formulations, aredisclosed in U.S. Pat. No. 4,261,868. Enzymes for use in detergents canbe stabilized by various techniques. Enzyme stabilisation techniques aredisclosed and exemplified in U.S. Pat. No. 3,600,319 and EP 0 199 405.Enzyme stabilisation systems are also described, for example, in U.S.Pat. No. 3,519,570.

Enzyme Stabilizers

The enzymes employed herein are stabilized by the presence ofwater-soluble sources of calcium and/or magnesium ions in the finishedcompositions which provide such ions to the enzymes. (Calcium ions aregenerally somewhat more effective than magnesium ions and are preferredherein if only one type of cation is being used.) Additional stabilitycan be provided by the presence of various other art-disclosedstabilizers, especially borate species: see Severson, U.S. Pat. No.4,537,706. Typical detergents, especially liquids, will comprise from 1to 30, preferably from 2 to 20, more preferably from 5 to 15, and mostpreferably from 8 to 12, millimoles of calcium ion per liter of finishedcomposition. This can vary somewhat, depending on the amount of enzymepresent and its response to the calcium or magnesium ions. The level ofcalcium or magnesium ions should be selected so that there is alwayssome minimum level available for the enzyme, after allowing forcomplexation with builders, fatty acids, etc., in the composition. Anywater-soluble calcium or magnesium salt can be used as the source ofcalcium or magnesium ions, including, but not limited to, calciumchloride, calcium sulfate, calcium malate, calcium maleate, calciumhydroxide, calcium formate, and calcium acetate, and the correspondingmagnesium salts. A small amount of calcium ion, generally from 0.05 to0.4 millimoles per liter, is often also present in the composition dueto calcium in the enzyme slurry and formula water. In solid detergentcompositions the formulation may include a sufficient quantity of awater-soluble calcium ion source to provide such amounts in the laundryliquor. In the alternative, natural water hardness may suffice.

It is to be understood that the foregoing levels of calcium and/ormagnesium ions are sufficient to provide enzyme stability. More calciumand/or magnesium ions can be added to the compositions to provide anadditional measure of grease removal performance.

The compositions herein may also optionally, but preferably, containvarious additional stabilizers, especially borate-type stabilizers.Typically, such stabilizers will be used at levels in the compositionsfrom 0.25% to 10%, preferably from 0.5% to 5%, more preferably from0.75% to 3%, by weight of boric acid or other borate compound capable offorming boric acid in the composition (calculated on the basis of boricacid). Boric acid is preferred, although other compounds such as boricoxide, borax and other alkali metal borates (e.g., sodium ortho-, meta-and pyroborate, and sodium pentaborate) are suitable. Substituted boricacids (e.g., phenylboronic acid, butane boronic acid, and p-bromophenylboronic acid) can also be used in place of boric acid.

Polymeric Dispersing Agents

Polymeric dispersing agents can be utilized at levels from 0.1% to 7%,by weight, in the compositions herein.

A polymeric material which can be included is polyethylene glycol (PEG).PEG can exhibit dispersing agent performance as well as act as a claysoil removal-antiredeposition agent. Typical molecular weight ranges forthese purposes range from 500 to 100,000, preferably from 1,000 to50,000, more preferably from 1,500 to 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of 10,000.

Clay Soil Removal/Anti-redeposition Agents

The compositions of the present invention can also optionally containwater-soluble ethoxylated amines having clay soil removal andantiredeposition properties. Granular detergent compositions whichcontain these compounds typically contain from 0.01% to 10.0% by weightof the water-soluble ethoxylates amines; liquid detergent compositionstypically contain 0.01% to 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. Another type of preferred antiredeposition agentincludes the carboxy methyl cellulose (CMC) materials. These materialsare well known in the art.

Polymeric Soil Release Agent

Any polymeric soil release agent known to those skilled in the art canoptionally be employed in the compositions and processes of thisinvention. Polymeric soil release agents are characterized by havingboth hydrophilic segments, to hydrophilize the surface of hydrophobicfibers, such as polyester and nylon, and hydrophobic segments, todeposit upon hydrophobic fibers and remain adhered thereto throughcompletion of washing and rinsing cycles and, thus, serve as an anchorfor the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerization of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerization of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to 30 oxypropylene units wherein said mixture contains asufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least 25% oxyethylene units and more preferably,especially for such components having 20 to 30 oxypropylene units, atleast 50% oxyethylene units; or (b) one or more hydrophobe componentscomprising (i) C₃ oxyalkylene terephthalate segments, wherein, if saidhydrophobe components also comprise oxyethylene terephthalate, the ratioof oxyethylene terephthalate:C₃ oxyalkylene terephthalate units is 2:1or lower, (ii) C₄ -C₆ alkylene or oxy C₄ -C₆ alkylene segments, ormixtures therein, (iii) poly (vinyl ester) segments, preferablypolyvinyl acetate), having a degree of polymerization of at least 2, or(iv) C₁ -C₄ alkyl ether or C₄ hydroxyalkyl ether substituents, ormixtures therein, wherein said substituents are present in the form ofC₁ -C₄ alkyl ether or C₄ hydroxyalkyl ether cellulose derivatives, ormixtures therein, and such cellulose derivatives are amphiphilic,whereby they have a sufficient level of C₁ -C₄ alkyl ether and/or C₄hydroxyalkyl ether units to deposit upon conventional polyestersynthetic fiber surfaces and retain a sufficient level of hydroxyls,once adhered to such conventional synthetic fiber surface, to increasefiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from 200, although higher levels can be used,preferably from 3 to 150, more preferably from 6 to 100. Suitable oxy C₄-C₆ alkylene hydrophobe segments include, but are not limited to,end-caps of polymeric soil release agents such as MO₃ S(CH₂)_(n) OCH₂CH₂ O--, where M is sodium and n is an integer from 4-6, as disclosed inU.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosicpolymers,copolymeric blocks of ethylene terephthalate or propyleneterephthalate with polyethylene oxide or polypropylene oxideterephthalate, and the like. Such agents are commercially available andinclude hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosicsoil release agents for use herein also include those selected from thegroup consisting of C₁ -C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S.Pat. No. 4,000,093, issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from 25,000 to 55,000. See U.S. Pat. No. 3,959,230 toHays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issuedJul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from Dupont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymeric soil release agents include the terephthalate polyesters ofU.S. Pat. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, the anionicend-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26,1988 to Gosselink, and the block polyester oligomeric compounds of U.S.Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoarolyl, end-cappedterephthalate esters.

If utilized, soil release agents will generally comprise from 0.01% to10.0%, by weight, of the detergent compositions herein, typically from0.1% to 5%, preferably from 0.2% to 3.0%.

Still another preferred soil release agent is an oligomer with repeatunits of terephthaloyl units, sulfoisoterephthaloyl units,oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form thebackbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units,oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from 1.7 to1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent alsocomprises from 0.5% to 20%, by weight of the oligomer, of acrystalline-reducing stabilizer, preferably selected from the groupconsisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, andmixtures thereof.

Dye Transfer Inhibiting Agents

The compositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process. Generally, such dye transferinhibiting agents include polyvinyl pyrrolidone polymers, polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents typically comprise from 0.01% to 10% by weight of thecomposition, preferably from 0.01% to 5%, and more preferably from 0.05%to 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R--A_(x)--P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N═; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR19## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa <10, preferably pKa <7, more preferred pKa <6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO". The most preferred polyamine N-oxide useful inthe detergent compositions herein is poly(4-vinylpyridine-N-oxide) whichas an average molecular weight of 50,000 and an amine to amine N-oxideratio of 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modem Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinyl-pyrrolidone ("PVP") having an average molecular weight of from5,000 to 400,000, preferably from 5,000 to 200,000, and more preferablyfrom 5,000 to 50,000. PVP's are known to persons skilled in thedetergent field; see, for example, EP-A-262,897 and EP-A-256,696.Compositions containing PVP can also contain polyethylene glycol ("PEG")having an average molecular weight from 500 to 100,000, preferably from1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basisdelivered in wash solutions is from 2:1 to 50:1, and more preferablyfrom 3:1 to 10:1.

The detergent compositions herein may also optionally contain from0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from 0.01% to 1%by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula: ##STR20## wherein R₁ is selectedfrom anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selectedfrom N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,chloro and amino; and M is a salt-forming cation such as sodium orpotassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is 4,4'-bis(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino!-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is 4,4'-bis(4-anilino-4-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino!2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is 4,4'-bis(4-anilino-6-morphilino-s-triazine-2-yl)amino!2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the "exhaustion coefficient". The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric "brightness" benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Conventional optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically from0.005% to 5%, preferably from 0.01% to 1.2% and most preferably from0.05% to 1.2%, by weight, into the detergent compositions herein.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, coumarin,carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.Examples of such brighteners are disclosed in "The Production andApplication of Fluorescent Brightening Agents", M. Zahradnik, Publishedby John Wiley & Sons, New York (1982). Further optical brightener whichmay also be used in the present invention include naphthlimide,benzoxazole, benzofuran, benzimidazole and any mixtures thereof.

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856. Thesebrighteners include the PHORWHITE series of brighteners from Verona.Other brighteners disclosed in this reference include: Tinopal UNPA,Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CCand Artic White CWD; the 2-(4-styryl-phenyl)-2H-naptho 1,2-d!triazoles;4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene;1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-styryl-naptho- 1,2-d!oxazole; and 2-(stilbene4-yl)-2H-naphtho1,2-d!triazole. See also U.S. Pat. No. 3,646,015.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the compositions of the present invention. Sudssuppression can be of particular importance in the so-called "highconcentration cleaning process" and in front-loading European-stylewashing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable saltsinclude the alkali metal salts such as sodium, potassium, and lithiumsalts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range of-40° C. and 50° C., and a minimum boiling point not less than 110° C.(atmospheric pressure). It is also known to utilize waxy hydrocarbons,preferably having a melting point below 100° C. The hydrocarbonsconstitute a preferred category of suds suppressor for detergentcompositions. Hydrocarbon suds suppressors are described, for example,in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al. Thehydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from 12 to 70carbon atoms. The term "paraffin," as used in this suds suppressordiscussion, is intended to include mixtures of true paraffins and cyclichydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to1,500 cs. at 25° C.;

(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resincomposed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in a ratio of from(CH₃)₃ SiO_(1/2) units and to SiO₂ units of from 0.6:1 to 1.2:1; and

(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solidsilica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from 0.001 to1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight% of said silicone suds suppressor, which comprises (1) a nonaqueousemulsion of a primary antifoam agent which is a mixture of (a) apolyorganosiloxane, (b) a resinous siloxane or a siliconeresin-producing silicone compound, (c) a finely divided filler material,and (d) a catalyst to promote the reaction of mixture components (a),(b) and (c), to form silanolates; (2) at least one nonionic siliconesurfactant; and (3) polyethylene glycol or a copolymer ofpolyethylene-polypropylene glycol having a solubility in water at roomtemperature of more than 2 weight %; and without polypropylene glycol.Similar amounts can be used in granular compositions, gels, etc. Seealso U.S. Pat. No. 4,978,471, Starch, issued Dec. 18, 1990, and U.S.Pat. No. 4,983,316, Starch, issued Jan. 8, 1991, U.S. Pat. No.5,288,431, Huber et al., issued Feb. 22, 1994, and U.S. Pat. Nos.4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 throughcolumn 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than 1,000, preferablybetween 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than 2 weight %, preferably more than 5weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than 1,000, more preferably between 100 and800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between 1:1 and 1:10, most preferablybetween 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆ -C₁₆alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a "suds suppressing amount. By "suds suppressing amount" is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to 5% of sudssuppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up to 5%,by weight, of the detergent composition. Preferably, from 0.5% to 3% offatty monocarboxylate suds suppressor is utilized. Silicone sudssuppressors are typically utilized in amounts up to 2.0%, by weight, ofthe detergent composition, although higher amounts may be used. Thisupper limit is practical in nature, due primarily to concern withkeeping costs minimized and effectiveness of lower amounts foreffectively controlling sudsing. Preferably from 0.01% to 1% of siliconesuds suppressor is used, more preferably from 0.25% to 0.5%. As usedherein, these weight percentage values include any silica that may beutilized in combination with polyorganosiloxane, as well as any adjunctmaterials that may be utilized. Monostearyl phosphate suds suppressorsare generally utilized in amounts ranging from 0.1% to 2%, by weight, ofthe composition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from 0.01% to 5.0%, although higher levels can be used.The alcohol suds suppressors are typically used at 0.2%-3% by weight ofthe finished compositions.

Fabric Softeners

Various through-the-wash fabric softeners, especially the impalpablesmectite clays of U.S. Pat. No. 4,062,647, Storm and Nirschl, issuedDec. 13, 1977, as well as other softener clays known in the art, canoptionally be used typically at levels of from 0.5% to 10% by weight inthe present compositions to provide fabric softener benefitsconcurrently with fabric cleaning. Clay softeners can be used incombination with amine and cationic softeners as disclosed, for example,in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 and U.S. Pat. No.4,291,071, Harris et al, issued Sep. 22, 1981.

Other Ingredients

A wide variety of other functional ingredients useful in detergentcompositions can be included in the compositions herein, including otheractive ingredients, carriers, hydrotropes, processing aids, dyes orpigments, solvents for liquid formulations, solid fillers for barcompositions, etc. If high sudsing is desired, suds boosters such as theC₁₀ -C₁₆ alkanolamides can be incorporated into the compositions,typically at 1%-10% levels. The C₁₀ -C₁₄ monoethanol and diethanolamides illustrate a typical class of such suds boosters. Use of suchsuds boosters with high sudsing adjunct surfactants such as the amineoxides, betaines and sultaines noted above is also advantageous. Ifdesired, soluble magnesium salts such as MgCl₂, MgSO₄, and the like, canbe added at levels of, typically, 0.1%-2%, to provide additional sudsand to enhance grease removal performance.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups(e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol)can also be used. The compositions may contain from 5% to 90%, typically10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Liquiddishwashing product formulations preferably have a pH between 6.8 and9.0. Laundry products are typically at pH 9-11. Techniques forcontrolling pH at recommended usage levels include the use of buffers,alkalis, acids, etc., and are well known to those skilled in the art.

Form of the Compositions

The detergent compositions of the invention can be formulated in anydesirable form such as powders, granulates, pastes, liquids, and gels.

Liquid Compositions

The detergent compositions of the present invention may be formulated asliquid detergent compositions. Such liquid detergent compositionstypically comprise from 94% to 35% by weight, preferably from 90% to 40%by weight, most preferably from 80% to 50% by weight of a liquidcarrier, e.g., water, preferably a mixture of water and organic solvent.

Gel Compositions

The detergent compositions of the present invention may also be in theform of gels. Such compositions are typically formulated with polyakenylpolyether having a molecular weight of from about 750,000 to about4,000,000.

Solid Compositions

The detergent compositions of the invention may also be in the form ofsolids, such as powders and granules.

The mean particle size of the components of granular compositions inaccordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.4 mm in diameter and not morethan 5% of particles are less than 0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves. The meanparticle size is taken to be the aperture size through which 50% byweight of the sample would pass.

The bulk density of granular detergent compositions in accordance withthe present invention are also useful in concentrated granular detergentcompositions that are characterised by a relatively high density incomparison with conventional laundry detergent compositions. Such highdensity compositions typically have a bulk density of at least 600g/liter, more preferably from 650 g/liter to 1200 g/liter, mostpreferably from 800 g/liter to 1000 g/liter.

Bulk density is measured by means of a simple funnel and cup deviceconsisting of a conical funnel moulded rigidly on a base and providedwith a flap valve at its lower extremity to allow the contents of thefunnel to be emptied into an axially aligned cylindrical cup disposedbelow the funnel. The funnel is 130 mm high and has internal diametersof 130 mm and 40 mm at its respective upper and lower extremities. It ismounted so that the lower extremity is 140 mm above the upper surface ofthe base. The cup has an overall height of 90 mm, an internal height of87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement eg; a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/liter.Replicate measurements are made as required.

Making Processes-Granular Compositions

In general, granular detergent compositions in accordance with thepresent invention can be made via a variety of methods including drymixing, spray drying, agglomeration and granulation.

The invention is illustrated in the following non limiting examples, inwhich all percentages are on a weight basis unless otherwise stated.

In the bleaching compositions of the invention, the abbreviatedcomponent identifications have the following meanings:

    ______________________________________    LAS       Sodium linear C.sub.12 alkyl benzene              sulphonate    TAS       Sodium tallow alcohol sulphate    C45AS     Sodium C.sub.14 -C.sub.15 linear alkyl sulphate    C45E7     A C.sub.14-15 predominantly linear primary alcohol              condensed with an average of 7 moles of              ethylene oxide    C25 E3    A C.sub.12-15 branched primary alcohol condensed              with an average of 3 moles of ethylene oxide    Nonionic  (hydroxyethyl dimethyl) ammonium quaternary    Silicate  Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O; 1.6              ratio)    NaSKS-6   Crystalline layered silicate of formula              δ-Na.sub.2 Si.sub.2 O.sub.5    Carbonate Anhydrous sodium carbonate with a particle size              between 200 μm and 900 μm    Sulphate  Anhydrous sodium sulphate    Zeolite A Hydrated Sodium Aluminosilicate of formula              Na.sub.12 (A10.sub.2 SiO.sub.2).sub.12.27H.sub.2 O              having a primary particle size in the range from              0.1 to 10 micrometers    MA/AA     Copolymer of 1:4 maleic/acrylic acid, average              molecular weight about 70,000.    PB4       Sodium perborate tetrahydrate of nominal              formula NaBO.sub.2.3H.sub.2 O.H.sub.2 O.sub.2    TAED      Tetraacetyl ethylene diamine    AvO.sub.2 Total amount of available oxygen present in the              composition    Brightener 1              Disodium 4,4'-bis(2-sulphostyryl)biphenyl    Brightener 2              Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-              triazin-2-yl)amino) stilbene-2:2'-disulphonate.    HEDP      Hydroxy-ethylene 1,1 diphosphonate    DTPMP     Diethylene triamine penta (methylene phosphonate),              marketed by Monsanto under the Trade name              Dequest 2060    EDDS      Ethylenediamine-N,N'-disuccinic acid,  S,S! isomer              in the form of the sodium salt.    Silicone antifoam              Polydimethylsiloxane foam controller with              Siloxane-oxyalkylene copolymer as dispersing              agent with a ratio of said foam controller to said              dispersing agent of 10:1 to 100:1.    Photoactivated              Sulphonated Zinc Phthalocyanine encapsulated in    bleach    dextrin soluble polymer    Savinase  proteolytic enzyme of activity 13 KNPU/g    Carezyme  cellulytic enzyme of activity 1000 CEVU/g    Termamyl  Amylolytic enzyme of activity 60 KNU/g    Lipolase  Lipolytic enzyme of activity 100 kLU/g    Endolase  Endoglunase A              all sold by NOVO Industries A/S    PVNO      Polyvinylpyridine N-oxide    PVPVI     Copolymer of polyvinylpyrolidone and              vinylimidazole    CMC       Sodium carboxymethyl cellulose    Metolose  Carboxy methoxy ether    SRA       Sulfobenzoyl end capped esters with              oxyethylene    (Soil Release              oxy and terephthaloyl backbone    Agent)    ______________________________________

EXAMPLE 1

The following formulations were prepared, where A and B are in accordwith the invention and 1 and 5 are prior art compositions.

200 g from each formulations A,B and 1 to 5 was taken and subjected eachto a full scale washing machine test using a Miele automatic washingmachine (Model WM W698) set to the short wash cycle at 40° C. for eachformulation. Water of 12° German hardness (=1.8 mol Ca²⁺ /liter) wasused.

    ______________________________________    Component    (% by weight)                A      B      1    2    3    4    5    ______________________________________    LAS         5.4    5.4    5.4  5.4  5.4  5.4  5.4    TAS         1.9    1.9    1.9  1.9  1.9  1.9  1.9    C25 E3      4.0    4.0    4.0  4.0  4.0  4.0  4.0    nonionic     0.60   0.60   0.60                                    0.60                                         0.60                                              0.60                                                   0.60    Zeolite A   19.1   19.1   15.5 15.5 15.5 15.5 15.5    MA/AA       0.3    0.3    2.8  2.8  2.8  2.8  2.8    PB4          9.25   9.25  14.1 14.1 14.1 14.1 14.1    TAED        1.8    1.4    1.6  --   1.8  1.0  2.5    AvO2         1.02   0.93   1.43                                    1.53                                         1.87                                              1.59                                                   2.11    Carbonate   20.5   20.5   18.6 18.6 18.6 18.6 18.6    silicate    2.8    2.8    4.7  4.7  4.7  4.7  4.7    Savinase Protease                 0.28   0.33   0.12                                    0.15                                         0.19                                              0.13                                                   0.28    Termamyl Amylase                 0.10   0.10  nil  nil  nil  nil  nil    DTPMP       0.3    0.3    0.3  0.3  0.3  0.3  0.3    HEDP        0.2    0.2    nil  nil  nil  nil  nil    ______________________________________     Minors and miscellaneous to balance

Two swatches demonstrating differing degrees of soil removal performancewere used as standard to establish a 4 point scale in which `+`represents a very poor soil removal performance and `+++` average soilremoval performance.

The two standards are used to define the mid points between the variousdescriptions of soil removal performance, viz

+ very poor soil removal performance

++ poor soil removal performance

+++ average soil removal performance

++++ good soil removal performance

Two expert panellists are used and their results are averaged.

The results are as follows:

    ______________________________________            A     B       1      2    3    4    5    ______________________________________    Stain removal              ++++    ++++    +    +    +    +    ++    performance    ______________________________________

It is seen that Compositions A and B produce enhanced stain removalperformance over the prior art Compositions 1 to 5.

EXAMPLE 2

The following base granule was prepared:

    ______________________________________    Components         % by weight    ______________________________________    LAS/TAS            6.0/2.0    C45 E7             4.0    nonionic           1.5    Zeolite A          20.0    PB4                8.0    TAED               1.2    Silicate (2.0 ratio)                       2.8    Savinase protease (4 knpu/g)                       0.8    DTPMP              0.3    ______________________________________     Minors and miscellaneous to balance

The following fractions were then incorporated in the base granule,where C is in accord with the invention and 6 and 7 are prior artcompositions.

    ______________________________________    Components    C           6      7    ______________________________________    MA/AA         0.9         2.8    4.5    Termamyl amylase                  0.1         0.1    0.1    Carbonate     20.0        20.0   20.0    HEDP           0.22       --     --    ______________________________________

200 g of each formulation were taken and placed into a Miele (W698)machine at 90° C. in 25° H water (5:1 Ca:Mg) together with white terryswatches and 2.5 kg of proteinaceous soiled laundry. For eachformulations, 50 cycles were run. At the end of the test, the whiteswatches were graded and samples analysed for total ash and metalcontent.

It was seen that composition C produced better soil removal and lessencrustation than compositions 6 and 7.

EXAMPLE 3

The following detergent compositions according to the invention wereprepared:

    ______________________________________    Components        D       E    ______________________________________    LAS               8.0     8.0    C25 E3             4.10    4.10    Zeolite A         12.0    19.10    Na SKS-6           6.16   --    MA/AA              1.50    0.30    SRA                0.10   --    Metolose           0.30   --    PVNO/PVPVI         0.02   --    Carbonate         20.50   20.5    Silicate          --       2.82    PB4               12.0     9.25    AvO.sub.2          1.25    0.96    TAED               1.85    1.85    EDDS               0.19   --    DTPMP             --       0.25    HEDP               0.20    0.22    MgSO.sub.4         0.30    0.30    Savinase protease  0.50    0.28    Lipolase lipase    0.12   --    Termamyl amylase   0.38    0.10    Carezyme Cellulase                       0.08   --    Endolase           0.08   --    CMC               --       0.22    Brightener 1       0.12   --    Brightener 2      --       0.11    Photoactivated bleach                       0.003  15 ppm    Silicone antifoam  0.10    0.55    Sulphate          24.0    25.88    Perfume            0.25    0.27    ______________________________________     Minors and miscellaneous to balance

The above formulations was seen to produce enhanced soil removalperformance and reduced encrustation.

What is claimed is:
 1. A non-phosphate builder-containing detergentcomposition comprising a surfactant, a water-soluble organic polymericpolycarboxylic compound, a chelant, an amylase and a source ofalkalinity, whereina)--said water-soluble organic polymericpolycarboxylic compound is in an amount less than 3% by weight, b)--saidchelant is in an amount from 0.1% to 10% by weight, c)--said amylase isin an amount from 0.001% to 5% by weight, and d)--said alkalinity sourcehas the capacity to deliver alkalinity to a wash solution as measured bythe alkalinity release test described herein, such that the % weightNaOH equivalent of the composition is greater than 8.0% by weight of thecomposition, provided that said water-soluble organic polymericpolycarboxylic compound and said alkalinity source are present in aweight ratio of 0.0732:1 or less.
 2. A detergent composition accordingto claim 1, wherein said chelant is selected from organic phosphonates,amino carboxylates, polyfunctionally-substituted aromatic chelatingagents, nitriloacetic acid and mixtures thereof.
 3. A detergentcomposition according to claim 2, wherein said chelant is an organicphosphonate chelant selected from α-hydroxy-2 phenyl ethyldiphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene,vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate andhydroxy-ethylene 1,1 diphosphonate.
 4. A detergent composition accordingto claim 2, wherein said chelant is hydroxy-ethylene 1,1 diphosphonate.5. A detergent composition according to claim 3, wherein saidpolycarboxylic compound is a co-polymeric polycarboxylic acid havingmonomeric unit selected from acrylic acid, maleic acid, fumaric acid,itaconic acid, aconitic acid, mesaconic acid, citraconic acid andmethylenemalonic acid and mixtures thereof.
 6. A detergent compositionaccording to claim 5, wherein said polycarboxylic compound is in amountless than 1% by weight.
 7. A detergent composition according to claim 5,wherein said amylase is selected from the group consisting ofα-amylases.
 8. A detergent composition according to claim 7 wherein saidcomposition further comprises a protease in amount from 0.001% to 5% byweight.
 9. A non-phosphate builder-containing detergent compositioncomprising a surfactant, a source of hydrogen peroxide, a water-solubleorganic polymeric polycarboxylic compound, a chelant, an amylase and asource of alkalinity, whereina)--said water-soluble organic polymericpolycarboxylic compound is in an amount less than 3% by weight, b)--saidchelant is in an amount from 0.1% to 10% by weight, c)--said amylase isin an amount from 0.001% to 5% by weight, and d)--said alkalinity sourcehas the capacity to deliver alkalinity to a wash solution as measured bythe alkalinity release test described herein, such that the % weightNaOH equivalent of the composition is greater than 8.0% by weight of thecomposition, provided that said water-soluble organic polymericpolycarboxylic compound and said alkalinity source are present in aweight ratio of 0.0732:1 or less.
 10. A detergent composition accordingto claim 9, wherein said chelant is an organic phosphonate chelantselected from the group consisting of α-hydroxy-2 phenyl ethyldiphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene,vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate andhydroxy-ethylene 1,1 diphosphonate.
 11. A detergent compositionaccording to claim 9, wherein said polycarboxylic compound is aco-polymeric polycarboxylic acid having monomeric unit selected from thegroup consisting of acrylic acid, maleic acid fumaric acid, itaconicacid, aconitic acid, mesaconic acid, citraconic acid andmethylenemalonic acid and mixtures thereof.
 12. A detergent compositionaccording to claim 11, wherein said polycarboxylic compound is in amountless than 1% by weight.
 13. A detergent composition according to claim11, wherein said detergent composition further comprises a protease inamount from 0.001% to 5% by weight.
 14. A detergent compositionaccording to claim 13, wherein the source of hydrogen peroxide is aninorganic perhydrate selected from the group consisting of perboratetetrahydrate, perborate monohydrate, percarbonate and mixtures thereof.15. A detergent composition according to claim 14 wherein said detergentcomposition comprises a bleach precursor compound selected from thegroup consisting of bleach precursor compounds which comprise at leastone acyl group forming the peroxyacid moiety bonded to a leaving groupthrough an --O-- or --N-- linkage.
 16. A detergent composition accordingto claim 15, wherein said bleach precursor is N,N-N',N' tetra acetylethylene diamine.
 17. A detergent composition according to claim 16,wherein said bleach precursor compound is in amount from 0.5% to 2.5% byweight.
 18. A method for reducing fabric encrustation which comprisescontacting the fabric with an effective amount of an aqueous solution ofa non-phosphate builder-containing detergent composition formulated witha surfactant, a water-soluble organic polymeric polycarboxylic compound,a chelant, an amylase and a source of alkalinity, whereina)--saidwater-soluble organic polymeric polycarboxylic compound is in an amountless than 3% by weight, b)--said chelant is in an amount from 0.1% to10% by weight, c)--said amylase is in an amount from 0.001% to 5% byweight, and d)--said alkalinity source has the capacity to deliveralkalinity to a wash solution as measured by the alkalinity release testdescribed herein, such that the % weight NaOH equivalent of thecomposition is greater than 8.0% by weight of the composition, providedthat said water-soluble organic polymeric polycarboxylic compound andsaid alkalinity source are present in a weight ratio of 0.0732:1 orless.
 19. A method according to claim 18, wherein said detergentcomposition comprises a chelant selected from the group consisting oforganic phosphonates, amino carboxylates, polyfunctionally-substitutedaromatic chelating agents, nitriloacetic acid and mixtures thereof. 20.A method according to claim 19, wherein said chelant is an organicphosphonate chelant selected from the group consisting of α-hydroxy-2phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1diphosphonate and hydroxy-ethylene 1,1 diphosphonate.
 21. A methodaccording to claim 18, wherein said chelant is hydroxy-ethylene 1,1diphosphonate.
 22. A method according to claim 20, wherein saidpolycarboxylic compound is a co-polymeric polycarboxylic acid havingmonomeric unit selected from the group consisting of acrylic acid,maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid,citraconic acid and methylenemalonic acid and mixtures thereof.
 23. Amethod according to claim 22, wherein said polycarboxylic compound is inamount less than 1% by weight.
 24. A method according to claim 22,wherein said amylase is selected from the group consisting ofα-amylases.